Wrinkle resistant fabrics and products for producing same



WRHNKLE RESISTANT FABRICS AND PRODUCTS FOR PRODUCING SAME Rosser LeeWayland, .lr., Edgewood, Md., and Marks Purrington Underwood and GeorgeS. Y. Poon, Danville, Va., assignors to Dan River Mills, Incorporated,Danville, Va., a corporation of Virginia No Drawing. ApplicationDecember 9, 1955 Serial No. 552,231

19 Claims. (Cl. 260-676) )1 to make them wrinkle resistant.

It is an object of this invention to provide new chemicals which areuseful for treatment of textile fabrics and which serve as intermediatesin the production of chemicals useful for the production of non-chlorineretentive F cotton textile fabrics. It is also an object of thisinvention to provide a process for manufacturing new resinformingmaterials for use in the textile industry and elsewhere.

It is also an object of this invention to provide new chemicals whichare particularly useful for the production of textile fabrics in whichdegradation from chlorine retention is minimized and yellowing fromchlorine retention is avoided.

It is a further object of this invention to provide a process fortreating textile fabrics to produce wrinkle resistant properties withoutthe disadvantage of deleterious chlorine retention. It is a furtherobject of this invention to provide a cotton textile fabriccharacterized by high wrinkle resistance, good physical properties interms of tear strength and tensile strength and by strong resistance todeleterious action from chlorine bleaches. Other objects of theinvention will be apparent from the detailed specification.

According to the present invention, at least three mols, preferably 3.5mols, of dimethylol ethylene urea are reacted with one mol of melamineto produce an intermediate product (A) which is water-soluble and whichmay be used for the treatment of textile fabrics to produce wrinkleresistance. According to the preferred process of this invention, theintermediate product (A) is then reacted with from about one to six molsof form aldehyde to produce a final product (B) which is useful fortreating cotton textile fabrics to produce wrinkle resistance withoutthe disadvantages of deleterious chlorine retention.

Lesser quantities of formaldehyde do not appear to safeguard against theharmful effects of chlorine reten tion to an adequate extent. Largerquantities of formaldehyde have little beneficial effect, and a largeexcess of formaldehyde will lower the physical properties of the treatedfabric.

Both condensations may be carried out under acid, basic or neutralconditions. However, care must be exercised in operation on the acidside, as there is a strong tendency toward polymerization under suchconditions and the condensation reaction is rarely controllable at belowabout pH 6.5.

If resinification of either the intermediate or final condensationproducts of the invention is desired, it may be accomplished by furtherreaction on the acid side. If stable resin-forming products aredesire-d, the pH of the final product must be carried well to thealkaline side.

It is well to note at this point that there are two separate anddistinct dangers to be avoided in the preparation of these products. Oneof these dangers is polymerization. This may occur at any time after thefirst reaction is started, and may even occur after storage of thefinished products. Low pH favors polymerization which may take placerapidly if the pH is low enough or very slowly under borderlineconditions.

A small amount of polymerization may not be harmful. The evil effectsarefirst noted by a failure of the partially polymerized products to retaintheir water solubility on infinite dilution. A greater degree ofpolymerization results, of course, in solidification of the product.Obviously polymerization is irreversible.

The other danger is a stability problem, namely, one of precipitateformation in the stored reaction products of this invention. Thechemical nature of the problem is unknown, but whatever the reactionforproducing such precipitates, it appears to be reversible, as heatingthe precipitated product will clear it. However, heating the producteach time it is to be used is highly unsatisfac tory on a commercialbasis and precipitated products are generally considered unsatisfactory.discussion, the precipitate problem is also referred to as a stabilityproblem.

In the production of a chemical product (B) which will produce nonchlorine retentive textile fabrics, it is quite important to regulatethe conditions of reaction if one is to obtain a stable product which isinfinitely dilutable in water. There is a relatively narrow range ofreaction conditions which will permit the obtention of desiredproperties. In this connection, it should be remembered that there is afirst reaction (1) or condensation of one moi of melamine with 3.5 molsof dimethylol ethylene urea to form an intermediate product (A) and asecond reaction (2) of product (A) with 3 mols of formaldehyde to form afinal product (B).

As an example of the problems involved, under most conditions, if the pHof the reactions (1) or (2) is below about 6.2, the final product (B)will either become in-- soluble immediately or else will form a hazysolution when diluted with water, due to polymerization. the other hand,if reaction (1) is carried out at 200 F. for ten minutes at a high pH ofabout 10 to 11, the final product (B) will have only limited stabilitywith a precipitate coming out in increasing amounts after a few days.

The critical pH range of reaction (1) for obtaining satisfactorycommercial materials appears to be from about pH 6.5 to pH 8.5. Itshould be noted, however, that this range is not an absolutely constantone under all reaction conditions. The problem of precipitate formationin product (B) may be greatly alleviated by using conditions inreaction 1) which include refluxing an aqueous solution ofdimethylolethylene urea with melamine. On the other hand, theprecipitate formation is aggravated by finishing off the final product(B) at a pH higher than about 9.5 to 10. For example, if the finalproduct (B) is to be stored at pH 11, the critical pH range of theinitial reaction (1) to prevent precipitate formation is no longer fromabout pH 6.5 to pH 8.5, but rather from about pH 6.5 to pH 7.5.

It also appears that these critical pH conditions may be satisfied tosome extent by controlling only the pH of the second reaction (2),namely, the condensation of the first formed product (A) withformaldehyde. For 3 example, it appears that if dimethylolethylene ureais condensed with melamine at 200 C. for 15 minutes at pH 11, a stableproduct can still be obtained if this intermediate product (A) isreacted with 3 mols of formaldehyde at pH 6.5 to 7 to form product (B).

Thus, several factors including time, temperature and- Patented Mar. 22,196p In the following pH of both reactions (1) and (2), as well as thefinal pH of the product B have an influence on the stabilitycharacteristics of the final product B in terms of both precipitateformation and polymerization. It appears that the optimum conditions arereflux temperatures for about 15 minutes, or until the melaminedissolves, at about pH 8 for reaction (1), a, temperature of from aboutl60-180 F. for about 15 minutes at about pH 7.5 for reaction (2) and thefinal pH of product B should be adjusted to about pH 9 to 9.5.

It has been determined by extended experimental investigation that anyone of these conditions may be rather widely varied provided the otherconditions are appropriately adjusted. However, to obtain a stable,substantially unpolymerized product (B), it appears critical that thepilot either'reaction (l) or (2) be held within the range of pH. 6.5 to8.5, that reaction (1) be at a temperature from. about 180 F. to refluxfor a time sufficient to dissolveall the melamine, that reaction (2) beata temperature of from about 140 F. to 190 F., and that the final pH ofthe thus-formed product shall be from about pH 8 to pH 11.

Satisfactory wrinkle resistance can be obtained on textile fabrics witheither product (A) or (B) by impregnating cellulosic fabric with fromabout to of the condensationv product in the presence of a smallquantity of an acid or acid-forming catalyst and thereafter heating theimpregnated fabric to dry it and to cure the resin. To obtain the samedegree of wrinkle resistance withoutdangerfrom chlorine retentionnecessitates neutralizing the alkalinity of the fabric at some timeprior to the final cure, impregnating the fabric with about 5%. to 15%of the final condensation product (B) of the intermediate (A) withformaldehyde and heating the thus impregnated fabric to dry it and toimpart a hard cure to the resin.

Neutralization of the fabric can be accomplished by two means. Thefabric can be neutralized prior. to impregnation by treatment in an acidbath such as acetic acid solution or a mild sulfuric acid solution. Suchneutralization must be carefully carried out to assure that the fabriccontains no more than .l% residual alkali measured as sodium hydroxide.

Another method of neutralization is to determine the amount of residualalkali in the fabric to be treated and then add enoughcatalyst, inexcess of the amount required for catalysis, to neutralize the alkalifound on the fabric.

To obtain ahard cure one'must balance the conditions regulating curewhich include time, temperature and amount of catalyst used forcatalysis. The final regulation in the treating step in usuallyaccomplished, by regulating the time and temperature of the cure andraising he or the other as'required to producea fabric which has thedesired properties of resistance to the harmful elfects of chlorinebleach. Exceptionally high temperatures must be avoided to preventdamaging the fabric and unusually long cures are not commerciallyattractive.

In the reaction (l),of melamine with dimethylol ethylene urea, it isnecessary to use at. least three mols of I u the dimethylol ethyleneurea for each mol of melamine. If lesser quantities of dimethylolethylene urea are used, the melamine .will not. go intosolutionand it isdesirable to add at least three and'one-half mols of the dimethyioiethylene urea to avoid a tendency to. cloudiness. Addition of a largerquantity of'the dimethylol ethylene urea has no adverse effect on thephysical nature of the reaction product, but it doeshave an adverseeffect on the nature of textile fabrics treated with. the product inthat larger quantities of the dimethylol ethylene :urea appear to.lessen the desirable subjective. qualities of hand and the'like whichare characteristic .of melamine treated fabrics. Likewise,vthe'additional quantities of the dimethylol ethylene urea appear. tolower thetear strength of. the treated. fabric, and they appear to makethe 4 chemical product more sensitive to varied conditions of cure andless likely to produce uniformly satisfactory results in terms of thetreated fabrics resistance to the harmful effects of chlorine retention.

The exact nature of the reaction products of this invention has not beenfully determined, but it appears that the intermediate reaction product(A) of one mol of melamine with three mols of dimethylol ethylene ureahas the following formula:

It is further theorized that the second reaction; names ly, the reactionof the intermediate with formaldehydeforms a compound (B) having thefollowing formula:

Example I Eight hundred seventy-four pounds (3.0 mols) of a 50% solidssolution ofdimethylol ethylene urea were placed in a stainless steelreactionv kettle equipped with heating coils and. a stirrer. One hundredtwenty-six pounds (one mol) of melamine were added with stirring.Twenty-five percent sodium hydroxide solution was added until the pH ofthe mixture was 10.0 to 11.0 and the temperature was raised to 200 F.and maintained until the solution tended to clear, which was about 30mina utes after the. desired temperature had been reached.

This intermediate product (A) was cooled to F. and 243 pounds (3 mols)of formaldehyde (37%) were added. The solution was then heated to F. forabout fifteen minutes and wasthen neutralizedto about pH 8.5 to 9.5. Theproduct (B) thus formed was a clear. liquid. in water and about theviscosity of ethylene glycol.

Example 11 hydroxide solution was added to bring the pH .ofthe;

mixture. to 10-.ll.. Thetemperature was..raised.to:;200

F. and. maintainedmntilthe. solution. cleared; which was;

about, 15 :minutes after thedesired itemperature "had .been.

reached. The'resulting solutionwas substantially clear." andwater-solublqalthough on repeated runs,-.cloudiness it appeared to bestable and infinitely soluble could be detected occasionally. Thisintermediate prod? uct (A) was cooled to 150 F. and 243 pounds (3 mols)of formaldehyde (37%) were added. The solution was then heated to 180F., and about fifteen minutes later, it was completely clear. It wasthen neutralized back to about pH 8.5 to 9.5. The solution (B) appearedto be stable and infinitely soluble in water. However, on long standinga precipitate sometimes formed and though it could be dissolved byheating, the product was considered commercially undesirable. It hadabout the same viscosity and general appearance as the final product ofExample I. This example was repeated twice. once using one and onceusing two mols of formaldehyde instead of three mols. The results wereabout the same all three times.

Example III Seventeen hundred fifty pounds (6 mols) of a 50% solution ofdimethylol ethylene urea were placed in a stainless steel reactionkettle equipped with heating coils and a stirrer. One hundred twenty-sixpounds (1 mol) of melamine were added with stirring, and enough sodiumhydroxide was added to bring the pH to 10-11. The temperature was raisedto 200 F. and maintained until the solution cleared, which was aboutfifteen minutes after the desired temperature had been reached.

The resulting solution (A) was completely clear and water-soluble. Thisintermediate product (A) was cooled to 150 F. and 243 pounds (3 mols) offormaldehyde were added. The solution was then heated to 180 F. andabout minutes later it was neutralized back to about pH 8.5 to 9.5. Thesolution (B) appeared to be stable and infinitely soluble in Water. Ithad the same viscosity and general appearance of the final product ofExample 1.

Example IV An unsoured cotton fabric running about 4.5 yards per pound,which had been peroxide bleached and mercerized, was impregnated with awater solution containing 10% of the intermediate product (A) of ExampleII and 1 /z% of Catalyst AC (37% 2-methyl 2-aminopropanol-lhydrochloride). The fabric picked up about 65% of its weight of thesolution. It was then air dried and cured for 70 seconds at 180 F. Thefabric was wrinkle resistant and had good physical properties, but didnot show uniformly low resistance to chlorine degradation. However, thefabric did not yellow in the manner of those treated withmelamine-formaldehyde resin and subsequently treated with chlorine.

Example V i The process of Example IV was repeated on unsoured cloth,using the final product (B) of Example II in place of the intermediate(A). The results of Example IV were generally duplicated.

Example VI A bleached and mercerized cotton fabric containing about .3%alkali measured as sodium hydroxide was first soured in a 25% aceticacid solution until the residual alkali was only about .1% titrated assodium hydroxide. The fabric was then dried without further washing. Aportion of the fabric thus prepared .was treated with a solutioncontaining 11% of the intermediate product (A) of Example II and 1 /z%of Catalyst AC. The sample was air dried and heated to 180 C. for 70seconds. The thus treated fabric had a high degree of wrinkleresistance; had good physical properties in that it had lost little of.its tear strength and tensile strength; but it did not show uniformlygood resistance to chlorine when tested. by. the AATCC scorch testrnethod.- Like the .fabriclofExamplesIV and V, the product of thisexample did not yellow upon treatment with chlorine.

Example VII Another portion of the fabric prepared for Example VI wastreated in an identical manner except that the final product (B) ofExample II was used instead of the intermediate product (A). The thustreated fabric appeared to have the same properties as the fabrictreated in accordance with Example VI except that it showed uniformlyhigh resistance to chlorine degradation when tested by the AATCC scorchtest method (Tentative Test Method 69-52, entitled Damage Caused byRetained Chlorine). The same results were obtained with the productsmade according to the alternate procedures of Example II, exceptthat'the lesser quantities of formaldee hyde showed a slight tendency toreduce uniformity of the low damage from chlorine retention.

Example VIII Another portion of the fabric prepared for Example VI wastreated in exactly the same manner as in Example VI, except that thefinal product (B) of Example I was used instead of the intermediateproduct (A), of Example II. The thus treated fabric appeared to besubstantially identical to the fabric treated in accordance with ExampleVII, as all differences in test results were found to be within therange ofexperimental error.

Example IX Another portion of the fabric prepared for Example VI wastreated in exactly the same manner as in Example VI, except that thefinal product (B) of Example III was used instead of the intermediateproduct (A) of Example 11. The thus treated fabric appeared to besubstantially identical to the fabric treated in accordance with ExampleVII, as all differences in test results were found to be within therange of experimental error.

Example X A bleached and mercerized cotton fabric containing about .3%alkali titrated as sodium hydroxide was treated with a solutioncontaining 10% of the final reaction product (B) of Example II and about5.5 of Catalyst AC. The fabric picked up 70% of its weight of solutionand was then air dried. After drying, it was cured for 70 seconds at C.and tested. The fabric showed good wrinkle resistance, good physicalproperties and uniformly high resistance to chlorine degradation. It wasgenerally the same as the product of Example VII. 1

It has been determined that .13% Catalyst AC will neutralize about 01%NaOH on fabric at 70% pickup. Therefore 3.9% of Catalyst AC was requiredfor neutralization, and 1.6% was available for catalysis.

In the foregoing examples only Catalyst AC has been shown. Similarseries have been run with other catalysts, such as monoethanolaminehydrochloride, diammonium phosphate, ammonium chloride, and calciumchloride. These catalysts are well known in the textile industry, andthis invention is directed to a process using the known catalysts andnot to the catalyst per se.

By the same token, most of the examples refer to air drying the fabricand thereafter curing for 70 seconds at 180 C. These are standardconditions which have. been found most useful in testing theeffectiveness of resin-forming materials on textile fabrics. It is wellknown in the art to dry by many different methods and to cure by manydifferent techniques. The conventional curing times are normally fromabout one minute at: 360 F. to 5 minutes at about 280 F. This isstandard textile practice and the specific drying conditions and curingconditions form no part of the I present invention.

Example g 1 Onethousand forty pounds (3.5 mols) ofa 50% solids solutionof dimethylol ethylene urea in water and ethyl ene glycol were placed ina stainless steel reaction-kettle 2 equipped with heating coils and astirrer. One hundred twenty-six pounds (one mol) of melamine were addedwith stirring. The mixture was then adjusted to pH 6.5 to 6.8 by theaddition of dilute hydrochloric acid solution. The temperature of themixture was raised to 200 F. and was maintained for about five minutes.An intermediate condensation product was formed as evidenced by the factthat all of the melamine went into solution. This intermediate productwas cooled to 150 F. and 324 pounds (4 mols) of formaldehyde (37%) wereadded. The solution was then heated to 160 F. for about minutes, and wasthen neutralized to about pH 9.0 to 10.0. The product thus formed wasclear and infinitely dilutable with water. A shelf sample of thisproduct remained clear after two months without losing its infinitedilutability. The final product of this example was applied to cottontextile fabric in accordance with the procedure of Example X and thethus treated fabric was satisfactory in all respects, beingindistinguishable 'by test from the 'fabrics produced by the proceduresof Examples VII and X.

Example XII One thousand forty pounds (3.5 mols) of a 50% solution ofdimethylol ethylene urea in water and ethylene glycol were placed in astainless steel reaction kettle equipped with heating coils and astirrer. Onehundred twenty-six pounds (1 mol) "of melamine were addedwith stirring. The mixture was adjusted to pH 7.0 to 7.5 by the additionof dilute hydrochloric acid solution (or dilute sodium hydroxidesolution). The temperature was raised to 200 F. and was maintained forabout minutes at 200 F. An intermediate condensation product was formedas evidenced by the fact that all of the melamine went into solution.This intermediate product was cooled to 150 F. and 324 pounds (4 mols)of formaldehyde (37%) were added. The solution was then heated to 180 F.and about 10 minutes later it was neutralized to about pH -9.0 to 10.0.The final product appeared to be stable and infinitely soluble in water.A shelf sample of this product remained clear after two months withoutlosing its infinite dilutability. The final product 'of this example wasapplied to cotton textile fabric in accordance with the procedure ofExample X and the thus treated fabric was satisfactory in all .respects,being indistinguishable by test from the fabrics produced by theprocedures of Examples VII and X.

Example XIII Example XII was repeated using eight hundred seventy-fourpounds (3.0 mols) of a 50% solids solution of dimethylol ethylene ureainstead of one thousand forty pounds. A final product of about the sameappearance and stability was obtained as in Example XII. The productalso appeared equivalent to the product of Example XII in the treatmentof textile fabric.

Example K] V One thousand forty pounds (3.5 mols) of a 50% solutlOH'Ofdimethylol ethylene urea in water and ethylene glycol were placed in astainless steel reaction kettle equipped with heating coils, a stirrerand a reflux conand the temperature was maintained for "about 10minutes. It was then adjusted to pH 9.0 to 9.5. The final product hadabout" the same general propert es as the {a An inter products from theExamples 11 to 13 with respect to stability, clarity and textiletreatment.

Example XV One thousand forty pounds (3.5 mols) of a 50% solution ofdimethylol ethylene urea in water and ethylene glycol were placed in astainless steel reaction kettle equipped with heating coils, a stirrerand a reflux conintermediate condensation product was formed asevidanced by the fact that all of the melamine went into solution. Theintermediate product was cooled to F. and 243 pounds (3 mols) offormaldehyde (37%) were added. The solution was adjusted to pH 7 to 7.5using dilute hydrochloric acid solution, after which it was heated to'F. to F. for 10 minutes. The product was cooled and was neutralized topH 9 to 10. This final product was clear and infinitely dilutable withwater and remained so after two months. It was equivalent to theproducts of Examples 11 to 14 in the treatment of textile fabrics.

Example XVI Example XV was repeated under the same conditions exceptafter the addition of formaldehyde, the solution was adjusted to pH 10to 10.5. The final product had the same properties as the product fromExample XV.

Thus it will be seen that the present invention provides a novelmeans ofproducing wrinkle resistant fabrics and a novel means for producingwrinkle resistant fabrics which do not have either the undesirableproperties of degradation or yellowing from chlorine retention.

It will also be seen that the present invention provides novel chemicalsand novel means for producing chemicals which find utility in thetextile fields and in other fields in which resin-forming materials ofthe melamine-formaldehyde type resins and ethyleneurea-formaldehyde typeresins have heretofore been used.

We claim: V v

1. The process which comprises reacting one'mol of 'rnelamine with fromabout 3 to 6 mols of dimethylol ethylene urea, under alkaline conditionsat atemperature of from about F. to 220 F.

2. The process as set forth in claim 1., wherein, as an additional step,the thus formed product is reacted with frorn about 1-6 mols offormaldehyde under alkaline conditions at a temperature of from about160 F. to 220 F.

3. The heat condensation product of from about 3 to 6 mols of dimethylolethylene urea with one mol of melamine at a pH of at least 6.5.

4. The process which comprises condensing from about 3 to 6 molsdimethylolethylene urea with one mol melamine at a temperature fromabout 180 F. to reflux for a time suifici'cnt to dissolve the melamineat from about pH 6.5 to pH 8.5, condensing the thus formed product withfrom about 1 to 6 mols formaldehyde at from about 160 F. to 180 F. forfrom about 10 to 30 minutes andth'ereaftcr adjusting the pH of the finalproduct to from about 8 to 11.

5. The process which comprises condensing about 3 to 6 molsdimethylolethylene urea with one mol melamine at a temperature of from180 F. to refiux'at from about pH 6.5 to 8.5, condensing the thus formedproduct with fromabout 1 to 6 mols formaldehyde at from about 160 F. to"180FL for'ifrom about 10 to 30 minutes at from about pH 6.5 to 'pH- 11,and thereafter adjusting the-pH of the final productlto from about pH 8to pH 11.

6. 'The' process which comprises condensing about 3.5 molsdirn'ethylole'thyl'ene urea with one mol melamine at a temperature offrom about 180 F. to reflux at from about pH 6.5 to pH 8.5, condensingthe thus formed product with about 4 mols formaldehyde at from about 160F. to 180 F. for from about to 30 minutes at from about pH 6.5 to pH 11,and thereafter adjusting the pH of the final product to from about pH 8to pH 11.

7. The process which comprises condensing about 3.5 molsdimethylolethylene urea with one mol melamine at reflux at from about pH6.5 to pH 8.5, condensing the thus formed product with from about 1 to 6mols formaldehyde at from about 160 F. to 180 F. for from about 10 to 30minutes at from about pH 6.5 to pH 8.5 and thereafter adjusting the pHof the final product to about 9.5.

8. The process which comprises condensing from about 3 to 6 mols ofdimethylolethylene urea with 1 mol of melamine at a pH of about 6.5 to8.5 and thereafter condensing the thus formed product with about 1 to 6mols of formaldehyde.

9. The process which comprises condensing from about 3 to 6 mols ofdimethylolethylene urea with 1 mol of melamine and thereafter condensingthe thus formed product with about 1 to 6 mols of formaldehyde at a pHof about 6.5 to 8.5.

10. A stable water soluble condensation product of the process claimedin claim 8.

11. A stable water soluble condensation product of the process claimedin claim 9.

12. The process of condensing from about 3 to 6 mols ofdimethylolethylene urea with 1 mol of melamine at a pH of 6.5 to 8.5 andthereafter condensing the thus formed product with about 1 to 6 mols offormaldehyde at a pH of about 6.5 to 8.5.

13. The process which comprises condensing about 3 to 6 molsdimethylolethylene urea with 1 mol melamine at a temperature of from 180F. to reflux at from about pH 6.5 to pH 11, condensing the thus formedproduct with from about 1 to 6 mols formaldehyde at from about 160 F. to180 F. for from about 10 to 30 minutes at from about pH 6.5 to pH 8.5,and thereafter adjusting the pH of the final product to from about pH 8to pH 11.

14. The process which comprises condensing about 3.5 molsdimethylolethylene urea with 1 mol melamine at a temperature of fromabout 180 F. to reflux at from about pH 6.5 to pH 11, condensing thethus formed 10 product with about 4 mols formaldehyde at from about F.to F. for from about 10 to 30 minutes at from about pH 6.5 to pH 8.5,and thereafter adjusting the pH of the final product to from about pH 8to pH 11.

15. The process as set forth in claim 2 in which the the fabric and curethe resin, that improvement which comprises substantially neutralizingthe alkali in the fabric prior to completion of the cure and using asthe resin-forming material the product produced in accordance with claim2. p

17. The process as set forth in claim 16 wherein said neutralization isaccomplished by acidification of the fabric prior to impregnation withthe resin solution.

18. -The process as set forth in claim 16 wherein said neutralization isaccomplished by using, in addition to the usual catalyst concentration,an excess of acidforming catalyst, the excess being that amount requiredto neutralize substantially all the alkali in the fabric.

19. The process as set forth in claim 16 wherein the catalyst is anamine hydrochloride.

References Cited in the file of this patent UNITED STATES PATENTS2,328,425 DAlelio Aug. 31, 1943 2,380,239 Howald July 10, 1945 2,548,416Barsky Apr. 10, 1951 2,690,404 Spangler et al Sept. 28, 1954 2,764,573,Reibnitz et al Sept. 25, 1956 OTHER REFERENCES Evans et al.: Abstract ofapplication Ser. No. 576,508, published Nov. 1, 1949.

1. THE PROCESS WHICH COMPRISES REACTING ONE MOL OF MELAMINE WITH FROMABOUT 3 TO 6 MOLS OF DIMETHYLOL ETHYLENE UREA, UNDER ALKALINE CONDITIONSAT A TEMPERATURE OF FROM ABOUT 180*F. TO 220*F.